CN109851801A - A kind of preparation and its application of the reverse phase of dendrimer modification/strong anion exchange mixed mode polymer - Google Patents
A kind of preparation and its application of the reverse phase of dendrimer modification/strong anion exchange mixed mode polymer Download PDFInfo
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Abstract
The present invention provides a kind of reverse phase for preparing dendrimer modification/strong anion exchange mixed mode adsorbent methods and applications.Specially crosslinking agent, function monomer, initiator are dissolved in pore-foaming agent, are passed through nitrogen deoxygenation, solution A are prepared, by nano-SiO2It is distributed in triton x-100 aqueous solution, obtains solution B, solution A and solution B are mixed, refiner dispersion simultaneously polymerize at 60 DEG C, obtained surface package SiO2Polymer and ethylenediamine in 80 DEG C of progress epoxy-amine ring-opening reactions, obtain the polymer with amido, remove SiO with hydrofluoric acid dips2Obtain G0-PGMA, then by two-step reaction dendrimer polyamide-amide (PAMAM) in G0-PGMA surface modification, mixed mode adsorbent is exchanged finally by the reverse phase/strong anion for obtaining dendrimer modification with the substance reaction with epoxy.
Description
Technical field
The invention belongs to environmental monitorings and field of new materials, and in particular to one kind has very high selectivity enriching and purifying weak acid
Property compound dendritic macromole modification reverse phase/strong anion exchange mixed mode polymer preparation and application.
Background technique
Sample pre-treatments are an important steps in analytic process.Biological sample (such as blood, serum and urine) and ring
The ingredients such as border sample, food samples are very complicated, and the content of target analytes is very low (ng/mL-μ g/mL), even if using high-resolution
The analysis instrument of rate, almost all of sample all cannot be analyzed directly.Therefore, the enrichment and purifying of sample are in sample analysis process
In it is most important.Common Sample Pretreatment Technique has liquid-liquid extraction, Solid Phase Extraction, pressurized liquid extraction etc..Solid Phase Extraction by
The advantages that high, organic solvent consumes less, is easy to operate in its extraction efficiency, reproducible is current most widely used sample
Pretreatment technology.
Solid phase extraction filler is many kinds of, but mainly reverse phase retention mechanism (such as C18, St-DVB), is relatively specific for parent
The enrichment of the target analytes of rouge oleophylic.There is hydrophilic-lipophilic balance (HLB) (HLB) material excellent reverse phase retention mechanism and water to soak
Property, improve the extraction efficiency to polarity object.But these materials all lack selectivity to target analytes.Reverse phase/from
The sorbent material of son exchange mixed mode incorporates two kinds of retention mechanisms of reverse phase and ion exchange, being capable of selective retention target
Analyte more effectively removes the interfering substance coexisted in matrix.
Polyamide-amide (PAMAM) dendrimer is a kind of novel tree-like macromolecular for synthesizing and rapidly developing in recent years
Polymer is one of current most extensive, the most in-depth dendrimer of research.The fixation of its structure is regular, from center to external symmetry
It dissipates and highly branched.The important feature feature of PAMAM dendrimer is exactly internal with lar nanometric cavities and activity abundant
Site has good hydrophily.Therefore available with different purposes by the modification of the functional group to active site
Dendrimer.PAMAM nano-catalytic, drug delivery, chemical sensor, sewage treatment, in terms of have it is potential
Using by dendrimer in conjunction with polymer phase, the active site of polymer can be improved, enhance the reservation to target analytes
Ability is a new research field.
Drug has caused the concern of society as a kind of emerging pollutant.The drug exposure in human class of low dosage in environment
There is very big potential hazard with wild animal: (1) being likely to result in genocide, for example the cinereous vulture of India is double due to having used
The food of chlorine sweet smell acid pollution and mortality, anti-parasite medicine Yi Fulei element can reduce in animal wastes the type of insect and
Quantity；(2) fish to feminize, ethinylestradiol are a kind of contraceptives being widely used, scientific investigations showed that: low dosage it is female
Glycol exposure can influence the development of male fish, and long-term low dose exposure may make fish endangered.(3) cocktail effect.One
As experiment only probe into a kind of influence of drug to organism, and there are many drug in environment, when many drugs act on simultaneously
When organism, due to influencing each other, it is difficult to predict their harm.Therefore, the medicament categories and concentration detected in environment are extremely closed
It is important.
Most drug can ionize in water with acid or basic group.Such as the anti-anti-inflammatory of most non-steroidal
Medicine has carboxyl (pKa< 5), and Beta receptor blockers with the basic groups (pK such as amidoa>8).These substances are under the conditions of suitable pH
Ionizable, traditional sorbent material C18 is poor to the selectivity and reserve capability of this kind of target analytes, and the rate of recovery is low, does
It is more to disturb object.The shortcomings that in order to overcome conventional solid extraction stuffing, has developed reverse phase/ion exchange mixed mode polymer filler,
It can be prepared using different monomer and functionalized reagent with different ions cation exchange groups (such as carboxyl, sulfonic group, quaternary ammonium ion
Group, amido) sorbent material.According to the suitable reverse phase/ion exchange absorbent of the property of object selection and suitably
SPE condition can reduce matrix interference, improve the rate of recovery, reduce detection limit.
The present invention prepares polymer microballoon using Pickering emulsion polymerisation process, and preparation process is simple and efficient, polymer
Uniform particle sizes, size are controllable.Then keep surface one layer of PAMAM of growth of polymer microballoon tree-shaped big by the method being gradually grafted
It is anti-finally with epoxides such as butanediol diglycidyl ether or resorcinolformaldehyde resins epoxy-amine to occur for molecule
It should obtain reverse phase/strong anion exchange mixed mode adsorbent.The reverse phase of dendrimer modification/strong anion exchange mixing
The polymer material of mode is by the ion exchange capacity with superelevation, the clean-up effect of superelevation.Currently, it is tree-shaped to yet there are no PAMAM
The reverse phase of macromolecular modification/strong anion exchange mixed mode polymer material is complicated as solid phase extraction filler enrichment, purification
The report of acidic drug in sample substrate.
Summary of the invention
The object of the present invention is to provide the weak acidic drugs in a kind of pair of complex matrices, and there is very high selectivity to be enriched with, net
Change the methods for making and using same of the sample pre-treatments material of effect.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of reverse phase of dendrimer modification/strong anion exchange mixed mode polymer prepares obtain according to the following steps
:
(1) monomer, crosslinking agent and initiator are dissolved in porogen solutions, are prepared into solution A；Wherein monomer is methyl
Glycidyl acrylate (GMA)；Crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate, trimethylolpropane tris
One of methacrylate or pentaerythritol triacrylate or two kinds or more；Initiator is azodiisobutyronitrile；Pore
Agent is the mixture of toluene or toluene and 1- lauryl alcohol, toluene: 1- lauryl alcohol=1:0.35-0.5 (w/w)；Monomer: crosslinking agent:
Pore-foaming agent=1:0.5-4:2-6:0.012-0.073；Solution A is placed in ice bath, ultrasonic degassing 5-15min, then leads to nitrogen 5-
15min removes oxygen molecule；
(2) by nano-SiO2It is distributed in the triton x-100 aqueous solution that 10mL mass concentration is 0-0.2%, nano-
SiO2Concentration be 3-15mg/ml, ultrasonic 5-15min makes nano-SiO2Dispersion prepares solution B, and 3-5mL solution A is then added,
It is mixed using refiner, is sealed after the oxygen molecule then led in nitrogen 2-5min exclusion system, obtain Pickering lotion, it will
Obtained Pickering lotion polymerization reaction 12-36h at 50-70 DEG C；
(3) after reaction, it using centrifuge separation or suction filtration, obtains being coated with SiO2Polymer composite material
(PGMA-SiO2)；
(4) it sieves, settle, obtain the polymer that partial size is 38-63 μm；
(5) use the mixed liquor of one or more of methanol, acetonitrile, ethyl alcohol, acetone for Extraction solvent Soxhlet pumping
Mention PGMA-SiO2, extract 12-24 hours, remove unreacted substance and pore-foaming agent in polymer, in a vacuum drying oven 40-
60 DEG C of dry 12-24h；
(6) after extracting, polymer material and ethylenediamine are in the aqueous solution of 50%-90% ethyl alcohol in 60 DEG C -80 DEG C
3-5h is reacted, the polymer with amido is obtained, is labeled as G0-PGMA-SiO2；
(7) hydrofluoric acid dips G0-PGMA-SiO is used2Remove the SiO of material surface2, 12-24h is impregnated, deionization is then used
It is washed to neutrality, obtains G0-PGMA；
(8) Michael addition: G0-PGMA is taken to be dispersed in the methanol solution of 50%-80% polymethyl acrylate, G0-
The concentration of PGMA is 0.05g/ml-0.1g/ml, and after leading to nitrogen 20-30min, sealing reacts at room temperature 24-48h, obtains end official
The product for ester group can be rolled into a ball, G0.5-PGMA is labeled as, with methanol or ethanol washing G0.5-PGMA, 40-60 DEG C of vacuum drying 12-
24h；
(9) aminolysis reaction: taking PGMA to be dispersed in the methanol solution of 50%-80% ethylenediamine, and the concentration of G0.5-PGMA is
0.05g/ml-0.1g/ml, leads to the oxygen in nitrogen 20-30min in removing system, and sealing reacts at room temperature 24-48h, obtains end
End functional group is the product of amido, is labeled as G1.0-PGMA, dry with methanol or ethanol washing G1.0-PGMA, 40-60 DEG C of vacuum
Dry 12-24h；
(10) above-mentioned (8) Michael addition and (9) aminolysis reaction are repeated, the polyamide-amide of different algebra is prepared
(PAMAM) polymer material modified, is labeled as Gn-PGMA, and n is the positive integer greater than zero；
(11) Gn-PGMA prepared in step (10) is reacted with the compound with epoxy-functional, reaction temperature is
60-80 DEG C, the reaction time is that 5-10h polymerize to get to the reverse phase of dendrimer modification/strong anion exchange mixed mode
Object；
(12) reverse phase/strong anion of filtering dendrimer modification exchanges mixed mode polymer, is subsequently placed in vacuum
In 40-60 DEG C of dry 12-24h in drying box.
Nano-SiO used in the step (2)2Partial size be 12-50nm；
Step (2) solution A is added in solution B, and refiner is used to disperse with the revolving speed of 4000-10000rpm/min
0.5-3min forms lotion；
The mass concentration of hydrofluoric acid used is 20%-40% in the step (7)；
The step (8), (9), (10) are gradually grafted dendrimer PAMAM on the surface of polymer；Step (11) is anti-
The functional end-group of the polymer of the dendrimer modification of application is amido；Compound with epoxy-functional is 1,4 fourths
One or both of Hexanediol diglycidyl ether or resorcinolformaldehyde resin；
Alternatively property adsorbent exists the reverse phase of the dendrimer modification/strong anion exchange mixed mode polymer
The application of Acidic Compounds in enriching and purifying fluid sample.
Reverse phase/strong anion of the dendrimer modification exchanges mixed mode polymer filling out as solid-phase extraction column
Material is for the weak acidic drug in enriching and purifying drinking water, milk, river water, sewage, blood or urine.
The Acidic Compounds include but is not limited to brufen, naproxen, Ketoprofen, Diclofenac, mefenamic acid, support
Fenamic acid.
The invention has the advantages that not needing grinding sieve using polymer microballoon prepared by Pickering emulsion polymerisation process
Point, uniform particle sizes, preparation process is simple, and yield is high.Then the dendrimer that polymer is modified is modified anti-
Phase/strong anion exchange mixed mode polymer has the ion exchange capacity of active site abundant and superelevation.It is solid when being used as
When phase fiber material, by selecting suitable SPE condition, selectively retain the acidulous material in complex matrices.
Reverse phase/strong anion exchange mixed mode polymer is as adsorbent to brufen, naproxen, Ketoprofen, double chlorine
The Acidic Compounds such as fragrant acid have extremely strong selectivity.The reverse phase of dendrimer modification/ion exchange mixed mode polymerization
Alternatively property adsorbent can separate such compound object from its matrix, remove the interfering substance in matrix.It is used as
Sample pretreatment material can make target compound obtain the clean-up effect of ultrahigh-recovery-rate and superelevation.
Detailed description of the invention
Fig. 1 is the infrared spectroscopy of the PGMA of the dendrimer modification of the PGMA and different algebra in the embodiment of the present invention
Figure.
Specific embodiment
The reverse phase of dendrimer modification/strong anion exchange mixed mode polymer has very well Acidic Compounds
Selectivity and accumulation ability, can be used for urine, blood, in environment Ketoprofen, naproxen, brufen and Diclofenac selection
Property enrichment.
Embodiment 1
(1) preparation of polymer microballoon
By the glycidyl methacrylate (GMA) of 30mmol (4.10mL), 20mmol (2.85mL) divinylbenzene
It is dissolved into the porogen solutions containing 6.87g toluene with 60mg azodiisobutyronitrile, is prepared into solution A, solution is placed in ice bath
In, then ultrasonic degassing 10min leads to nitrogen 15min into solution A and removes oxygen molecule.By the nano-SiO of 80mg partial size 12nm2
It is distributed in the TritonX-100 aqueous solution that 10mL mass concentration is 0.02%, ultrasonic 10min allows nano-SiO2Dispersion, then
3mL solution A is added, 1min is stirred using refiner 6000rpm/min, after then leading to the air above nitrogen 3min removing system
Sealing, by obtained Pickering lotion 60 DEG C of polymerization reactions for 24 hours.It filters after reaction, then crosses 400 mesh and 230 mesh
Stainless steel sieve, then twice with acetone sedimentation, each 10min, obtaining partial size is 38-63 μm of polymer P GMA-SiO2.With first
Alcohol is Extraction solvent, carries out Soxhlet extraction for 24 hours, unreacted impurity and pore-foaming agent in polymer is removed, then in vacuum drying
60 DEG C of dry 12h in case.By 2g polymer microballoon PGMA-SiO2It is dispersed in the ethanol solution of 10mL 70%, 5mL second is added
Diamines is in 80 DEG C of reaction 3h.It filters after reaction, obtains the PGMA-SiO with amido functional group2Composite material is named as
G0-PGMA-SiO2, then use the hydrofluoric acid dips G0-PGMA-SiO of 10mL 40%2Remove the SiO on surface2, impregnate for 24 hours, so
After be washed with deionized water to neutrality, obtain polymer material G0-PGMA.The specific surface area and pore volume of G0-PGMA polymer are shown in
Table 1.
Embodiment 2
By the glycidyl methacrylate (GMA) of 30mmol (4.10mL), 20mmol (2.85mL) divinylbenzene
It is dissolved into the porogen solutions of containing toluene/1- lauryl alcohol (9/1, w/w) (6.87g), prepares with 60mg azodiisobutyronitrile
At solution A, solution is placed in ice bath, ultrasonic degassing 10min, is then led to nitrogen 15min into solution A and is removed oxygen molecule.It will
The nano-SiO of 80mg partial size 12nm2It is distributed in the TritonX-100 aqueous solution that 10mL mass concentration is 0.02%, ultrasound
5min allows nano-SiO2Then 3mL solution A is added in dispersion, stir 1min using refiner 6000rpm/min, then lead to nitrogen
Sealed after air above 3min removing system, by obtained Pickering lotion 60 DEG C of polymerization reactions for 24 hours.Reaction terminates
After filter, then cross the stainless steel sieve of 400 mesh and 230 mesh, then twice with acetone sedimentation, each 10min, obtaining partial size is 38-
63 μm of polymer P GMA-SiO2.Using methanol as Extraction solvent, Soxhlet extraction is carried out for 24 hours, remove unreacted miscellaneous in polymer
Matter and pore-foaming agent, then 60 DEG C of dry 12h in a vacuum drying oven.By 2g polymer microballoon PGMA-SiO2It is dispersed in 10mL
In 70% ethanol solution, 5mL ethylenediamine is added in 80 DEG C of reaction 3h.It filters, is obtained with amido functional group after reaction
PGMA-SiO2Composite material is named as G0-PGMA-SiO2, then use the hydrofluoric acid dips G0-PGMA-SiO of 10mL 40%2
Remove the SiO on surface2, impregnate for 24 hours, be then washed with deionized water to neutrality, obtain polymer material G0-PGMA.G0-PGMA is poly-
The specific surface area and pore volume for closing object are shown in Table 1.
Embodiment 3
By the glycidyl methacrylate (GMA) of 30mmol (4.10mL), 20mmol (2.85mL) divinylbenzene
It is dissolved into the porogen solutions of containing toluene/1- lauryl alcohol (7/3, w/w) (6.87g), prepares with 60mg azodiisobutyronitrile
At solution A, solution is placed in ice bath, ultrasonic degassing 10min, is then led to nitrogen 15min into solution A and is removed oxygen molecule.It will
The nano-SiO of 80mg partial size 12nm2It is distributed in the TritonX-100 aqueous solution that 10mL mass concentration is 0.02%, ultrasound
5min allows nano-SiO2Then 3mL solution A is added in dispersion, stir 1min using refiner 6000rpm/min, then lead to nitrogen
Sealed after air above 3min removing system, by obtained Pickering lotion 60 DEG C of polymerization reactions for 24 hours.Reaction terminates
After filter, then cross the stainless steel sieve of 400 mesh and 230 mesh, then twice with acetone sedimentation, each 10min, obtaining partial size is 38-
63 μm of polymer P GMA-SiO2.Using methanol as Extraction solvent, Soxhlet extraction is carried out for 24 hours, remove unreacted miscellaneous in polymer
Matter and pore-foaming agent, then 60 DEG C of dry 12h in a vacuum drying oven.By 2g polymer microballoon PGMA-SiO2It is dispersed in 10mL
In 70% ethanol solution, 5mL ethylenediamine is added in 80 DEG C of reaction 3h.It filters, is obtained with amido functional group after reaction
PGMA-SiO2Composite material is named as G0-PGMA-SiO2, then use the hydrofluoric acid dips G0-PGMA-SiO of 10mL 40%2
Remove the SiO on surface2, impregnate for 24 hours, be then washed with deionized water to neutrality, obtain polymer material G0-PGMA.G0-PGMA is poly-
The specific surface area and pore volume for closing object are shown in Table 1.
Embodiment 4
By the glycidyl methacrylate (GMA) of 30mmol (4.10mL), 20mmol (2.85mL) divinylbenzene
It is dissolved into the porogen solutions of containing toluene/1- lauryl alcohol (6/4, w/w) (6.87g), prepares with 60mg azodiisobutyronitrile
At solution A, solution is placed in ice bath, ultrasonic degassing 10min, is then led to nitrogen 15min into solution A and is removed oxygen molecule.It will
The nano-SiO of 80mg partial size 12nm2It is distributed in the TritonX-100 aqueous solution that 10mL mass concentration is 0.02%, ultrasound
5min allows nano-SiO2Then 3mL solution A is added in dispersion, stir 1min using refiner 6000rpm/min, then lead to nitrogen
Sealed after air above 3min removing system, by obtained Pickering lotion 60 DEG C of polymerization reactions for 24 hours.Reaction terminates
After filter, then cross the stainless steel sieve of 400 mesh and 230 mesh, then twice with acetone sedimentation, each 10min, obtaining partial size is 38-
63 μm of polymer P GMA-SiO2.Using methanol as Extraction solvent, Soxhlet extraction is carried out for 24 hours, remove unreacted miscellaneous in polymer
Matter and pore-foaming agent, then 60 DEG C of dry 12h in a vacuum drying oven.By 2g polymer microballoon PGMA-SiO2It is dispersed in 10mL
In 70% ethanol solution, 5mL ethylenediamine is added in 80 DEG C of reaction 3h.It filters, is obtained with amido functional group after reaction
PGMA-SiO2Composite material is named as G0-PGMA-SiO2, then use the hydrofluoric acid dips G0-PGMA-SiO of 10mL 40%2
Remove the SiO on surface2, impregnate for 24 hours, be then washed with deionized water to neutrality, obtain polymer material G0-PGMA.G0-PGMA is poly-
The specific surface area and pore volume for closing object are shown in Table 1.
Table 1 is the performance test results of the G0-PGMA of invention.
| Specific surface area (m2/g) | Kong Rong (cm3/g) | |
| Embodiment 1 | 169.4 | 0.565 |
| Embodiment 2 | 167.6 | 0.523 |
| Embodiment 3 | 121.6 | 0.442 |
| Embodiment 4 | 132.3 | 0.459 |
As can be seen from the table by changing the type of pore-foaming agent and the specific surface area of the adjustable PGMA polymer of ratio
And Kong Rong.
Embodiment 5
(1) polymer microballoon of PAMAM dendrimer modification
A.Michael addition: taking 2g G0-PGMA to be dispersed in 20mL, in the methanol solution of 60% polymethyl acrylate, leads to
Oxygen in nitrogen 30min removing system, sealing, room temperature reaction for 24 hours, obtain the polymer material that functional end-group is ester group,
It is denoted as G0.5-PGMA, with ethanol washing three times, 60 DEG C of vacuum drying 12h.B. aminolysis reaction: 2.0g G0.5-PGMA is dispersed
In 20mL, the methanol solution of 60% ethylenediamine, lead to the oxygen in nitrogen 30min in removing system, sealing reacts at room temperature for 24 hours,
The polymer that functional end-group is amino is obtained, G1.0-PGMA is named as.Repeat above-mentioned Michael addition and aminolysis reaction, system
The polymer material (Gn-PGMA, n=1,2,3 ...) that the PAMAM of standby different algebra is modified.
(2) reverse phase/strong anion exchange polymer microballoon preparation
It takes 2g Gn-PGMA to be dispersed in the ethanol solution of 10mL 70%, 5mL resorcinolformaldehyde resin is added,
In 80 DEG C of reaction 8h, reverse phase/strong anion exchange adsorbing substance (Gn of PAMAM modification is obtained+- PGMA), second is used after reaction
Alcohol washing, in 60 DEG C of vacuum drying 12h.
As can be seen from Figure 1 it is grown with PAMAM on the surface of PGMA, 1555cm-1And 1654cm-1Infrared absorption
Peak intensity enhancing, illustrates PAMAM in the surface PGMA successful growth.
Claims (6)
1. a kind of reverse phase of dendrimer modification/strong anion exchange mixed mode polymer preparation method, feature exist
In: it prepares according to the following steps:
(1) monomer, crosslinking agent and initiator are dissolved in porogen solutions, are prepared into solution A；Wherein monomer is metering system
Acid glycidyl ester (GMA)；Crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate, trimethylol propane trimethyl
One of acrylate or pentaerythritol triacrylate or two kinds or more；Initiator is azodiisobutyronitrile；Pore-foaming agent is
The mixture of toluene or toluene and 1- lauryl alcohol, toluene: 1- lauryl alcohol=1:0.35-0.5 (w/w)；Monomer: crosslinking agent: pore
Agent=1:0.5-4:2-6:0.012-0.073；Solution A is placed in ice bath, ultrasonic degassing 5-15min, then leads to nitrogen 5-15min
Remove oxygen molecule；
(2) by nano-SiO2It is distributed in the triton x-100 aqueous solution that 10mL mass concentration is 0-0.2%, nano-SiO2's
Concentration is 3-15mg/ml, and ultrasonic 5-15min makes nano-SiO2Dispersion prepares solution B, and 3-5mL solution A is then added, and uses
Then refiner mixing seals after the oxygen molecule in logical nitrogen 2-5min exclusion system, obtains Pickering lotion, will obtain
Pickering lotion at 50-70 DEG C polymerization reaction 12-36h；
(3) after reaction, it using centrifuge separation or suction filtration, obtains being coated with SiO2Polymer composite material
(PGMA-SiO2)；
(4) it sieves, settle, obtain the polymer that partial size is 38-63 μm；
(5) use the mixed liquor of one or more of methanol, acetonitrile, ethyl alcohol, acetone for Extraction solvent soxhlet type
PGMA-SiO2, extract 12-24 hours, remove unreacted substance and pore-foaming agent in polymer, in a vacuum drying oven 40-60
DEG C dry 12-24h；
(6) after extracting, polymer material reacts in the aqueous solution of 50%-90% ethyl alcohol in 60 DEG C -80 DEG C with ethylenediamine
3-5h obtains the polymer with amido, is labeled as G0-PGMA-SiO2；
(7) hydrofluoric acid dips G0-PGMA-SiO is used2Remove the SiO of material surface2, 12-24h is impregnated, is then washed with deionized water
To neutrality, G0-PGMA is obtained；
(8) Michael addition: taking G0-PGMA to be dispersed in the methanol solution of 50%-80% polymethyl acrylate, G0-PGMA's
Concentration is 0.05g/ml-0.1g/ml, and after leading to nitrogen 20-30min, sealing reacts at room temperature 24-48h, and obtaining functional end-group is
The product of ester group is labeled as G0.5-PGMA, with methanol or ethanol washing G0.5-PGMA, 40-60 DEG C of vacuum drying 12-24h；
(9) aminolysis reaction: taking PGMA to be dispersed in the methanol solution of 50%-80% ethylenediamine, and the concentration of G0.5-PGMA is
0.05g/ml-0.1g/ml, leads to the oxygen in nitrogen 20-30min in removing system, and sealing reacts at room temperature 24-48h, obtains end
End functional group is the product of amido, is labeled as G1.0-PGMA, dry with methanol or ethanol washing G1.0-PGMA, 40-60 DEG C of vacuum
Dry 12-24h；
(10) above-mentioned (8) Michael addition and (9) aminolysis reaction are repeated, the polyamide-amide (PAMAM) for preparing different algebra is repaired
The polymer material of decorations, is labeled as Gn-PGMA, and n is the positive integer greater than zero；
(11) Gn-PGMA prepared in step (10) is reacted with the compound with epoxy-functional, reaction temperature 60-80
DEG C, the reaction time is 5-10h to get the reverse phase modified to dendrimer/strong anion exchange mixed mode polymer；
(12) reverse phase/strong anion of filtering dendrimer modification exchanges mixed mode polymer, is subsequently placed in vacuum drying
In 40-60 DEG C of dry 12-24h in case.
2. reverse phase/strong anion of dendrimer modification according to claim 1 exchanges mixed mode polymer, special
Sign is:
Nano-SiO used in step (2)2Partial size be 12-50nm；
Step (2) solution A is added in solution B, and refiner is used to disperse 0.5-3min with the revolving speed of 4000-10000rpm/min
Form lotion；
The mass concentration of hydrofluoric acid used is 20%-40% in step (7)；
Step (8), (9), (10) are gradually grafted dendrimer PAMAM on the surface of polymer；The tree of step (11) reaction
The functional end-group of the polymer of shape macromolecular modification is amido；Compound with epoxy-functional is the contracting of 1,4 butanediols two
One or both of water glycerin ether or resorcinolformaldehyde resin.
3. reverse phase/strong anion that a kind of preparation method as claimed in claim 1 or 2 obtains dendrimer modification exchanges hybrid guided mode
Formula polymer.
4. a kind of reverse phase of the modification of dendrimer described in claim 3/strong anion exchange mixed mode polymer is as choosing
The application of selecting property adsorbent Acidic Compounds in enriching and purifying fluid sample.
5. reverse phase/strong anion of dendrimer modification exchanges the conduct of mixed mode polymer according to claim 4
The application of selective absorbent Acidic Compounds in enriching and purifying fluid sample, it is characterised in that: the dendrimer
The reverse phase of modification/strong anion exchange mixed mode polymer as the filler of solid-phase extraction column be used for enriching and purifying drinking water,
Weak acidic drug in milk, river water, sewage, blood or urine.
6. reverse phase/strong anion of dendrimer modification exchanges the conduct of mixed mode polymer according to claim 4
The application of selective absorbent Acidic Compounds in enriching and purifying fluid sample, it is characterised in that: the faintly acid chemical combination
Object includes but is not limited to brufen, naproxen, Ketoprofen, Diclofenac, mefenamic acid, tolfenamic acid.
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